CN1832908A - Process for activation of aif3 based catalysts and isomerization methods for chlorofluorocarbons - Google Patents
Process for activation of aif3 based catalysts and isomerization methods for chlorofluorocarbons Download PDFInfo
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- CN1832908A CN1832908A CNA2004800218063A CN200480021806A CN1832908A CN 1832908 A CN1832908 A CN 1832908A CN A2004800218063 A CNA2004800218063 A CN A2004800218063A CN 200480021806 A CN200480021806 A CN 200480021806A CN 1832908 A CN1832908 A CN 1832908A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
- C07C17/358—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by isomerisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/125—Halogens; Compounds thereof with scandium, yttrium, aluminium, gallium, indium or thallium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/22—Halogenating
- B01J37/26—Fluorinating
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Abstract
An activated AlF3 based catalyst is produced by treating a crude AlF3 for more than 5 hours with a gas stream at a temperature from 300 DEG C to 450 DEG C.
Description
Technical field
The present invention relates to produce active A lF
3The method of catalyzer, active A lF
3The method of catalyzer and isomerization Chlorofluorocarbons (CFCs).
The present invention is in particular to utilizing active catalyst with 1,1,2-three fluoro-1,2-ethylene dichloride (CF
2Cl-CHFCl hereinafter is called HCFC-123a or " asymmetric " isomer) isomery turns to 1,1,1-three fluoro-2,2-ethylene dichloride (CF
3-CHCl
2, hereinafter be called HCFC-123 or " symmetry " isomer) method.More specifically, the present invention relates to that low levels (is lower than 0.1% by making the HCFC-123a isomerization that contains in the 123/123a mixture obtain to have very, perhaps 1000ppm preferably is lower than 0.05%, perhaps 500ppm) the method for HCFC-123 of asymmetric isomer HCFC-123a.
As everyone knows, need there be a kind of commercial run, be used to prepare the HCFC-123 (for example, referring to United States Patent (USP) 5,600,037) that does not contain the 123a isomer as far as possible.
Yet, the commercial run for preparing HCFC-123 in the most frequently used being used for, promptly in the presence of suitable catalyzer, with HF tetrachloroethylene is fluoridized, product always contains the 123a isomer, its amount is from several thousand ppm to several parts of %: for example, referring to WO 95/32168, EP application 609123 (has also obtained 123b isomer C F
2H-CFCl
2, but amount is very little so that can ignore its existence).
Because physicochemical property similar (for example, 123 boiling point is 27.1 ℃, and the boiling point of 123a is 28.2 ℃) are very difficult with the physical method for separation isomer.
Having proposed several chemical processes handles the 123/123a mixture and changes into easier 123a and 123 isolating other compounds: for example, be disproportionated into HCFC-124 and HCFC-122 (United States Patent (USP) 5.414.167), fluoridize into HCFC-124 (United States Patent (USP) 5.773.671), dehydrochlorination becomes CTFE (chlorotrifluoroethylene), or the like.
Unfortunately, though in each method of these methods, the 123a isomer all is that tool is reactive in two kinds of compounds, and they do not have a large amount of losses that enough selectivity prevent the 123 symmetrical isomer of reaction along with the 123a reaction, although speed is lower.And, promptly enable to reach 100% selectivity, in any case 123a also will change into certain other compound and lose.
Therefore several methods of 123 that in liquid phase or gas phase the 123a catalytic isomerization turned to have been proposed.
Liquid phase homogeneous catalysis method is very effective usually in isomerization reaction, but also has several shortcomings, and wherein the most serious is, usually (for example cause low selectivity owing to forming several undesirable by products, referring to Jap.Appl.63-85175, Oct.16,1989); United States Patent (USP) 5,302 discloses in 766 and a kind ofly has more optionally liquid phase process, but the efficient of this method is very low: the best result of report is the duration of contact through a few hours, and residual have a 123a of 0.63%; More generally, compare with gas phase homogeneous catalysis method, the homogeneous phase liquid phase process needs more complicated and more expensive reaction product forming process.
United States Patent (USP) 5,600,037 discloses a kind of heterogeneous method, in the method, uses solid catalyst AlF
3(aluminum fluoride) be isomerization HCFC-123a in gas phase.Yet, in the patent of quoting, never obtain 123a and be less than 0.1% aforementioned target.
In fact, be lower than 0.1% product, need be in being lower than patent ' 037 embodiment carry out isomerization reaction under the temperature of temperature in order to obtain 123a content; This be because 123a be converted into 123 reaction be subjected to equilibrium-limited and isomer between the equilibrium constant help 123 at low temperatures, at high temperature help 123a.For example referring to United States Patent (USP) 5.302.766 (licensing to DuPont company), its result is confirmed by the data that the applicant obtains.
Therefore, in order to obtain to contain the product of low remaining quantity 123a, need carry out isomerization reaction at low temperatures; Yet, in this case, the very fast inactivation of catalyzer, it is short as to make us being difficult to accept to act on working lipe of steam: 123a changes into that 123 transformation efficiency reduces and remaining 123a in the exhaust vapour increases after a few hours, and considerably beyond desirable limit value: for example, this is disclosed in United States Patent (USP) 5,118, in 887, wherein in embodiment, only the transformation efficiency through 3 hours 123a just is reduced to 85% from 99.9% in steam; The applicant's oneself work has confirmed these data.
On the contrary, at high temperature inactivation is slower, but remaining 123a can not be lower than the balance limit: for example, in the time of 350 ℃, inactivation can be ignored but remaining 123a can not be lower than about 0.3% owing to the isomer balance.
At present, the applicant finds that surprisingly these problems can utilize based on aluminum trifluoride (AlF
3) catalyzer overcome, described catalyzer is handled in advance to use in the following manner.
Therefore, the present invention relates to produce active A lF
3Catalyst based method, wherein under 300 ℃～450 ℃ temperature, with air-flow to rough AlF
3Handle more than 5 hours.
When using the catalyzer that is obtained by this method, for example, in the gas phase isomerization reaction of Chlorofluorocarbons (CFCs) such as HCFC-123a, catalyst deactivation is very slow, regenerates between reactor only needs or ground.Active A lF
3Activity of such catalysts generally kept its initial level at least 10 hours.Usually its activity can keep 50 hours at least.In preferred embodiments, described active the maintenance at least 100 hours.In especially preferred embodiment, described active maintenance is more than 200 hours.
Aspect especially being included in the isomerization of the HCFC-123a among the HCFC-123, hydrochloric ether obtained fabulous result.At active A lF
3The isomer purity of the product after the existence of catalyzer is handled down is generally greater than 99.9 moles of %.Usually obtain being equal to or greater than the purity of 99.95 moles of %.
In this manual, " aluminum trifluoride (AlF
3) " be used for specifically refering in particular to crystalline solid with this chemical formula, obtain by (hydrogen) aluminum oxide (so-called alumina) being fluoridized fully usually with anhydrous hydrogen fluoride (HF), for example, described in United States Patent (USP) 6.187.280 and 6.432.362.Producing in the process of aluminum fluoride like this, partially fluorinated alumina more and more can not further react.Therefore, do not reach " the AlF of stoichiometry molecular formula usually with these methods
3".
The rough AlF that is used for the method according to this invention
3Generally contain the stoichiometry AlF of 90wt% at least
3Preferred stoichiometry AlF
3Content be 95wt% at least.More preferably stoichiometry AlF
3Content be 96wt% at least.The rough AlF that is used for the method according to this invention
3Generally contain the stoichiometry AlF of 99.9wt% at the most
3Usually, stoichiometry AlF
3Content be 99wt% at the most.
Record the rough AlF that is used for the method according to this invention with the nitrogen adsorption method
3Generally has the 15m of being equal to or greater than
2The B.E.T. specific surface area of/g.Usually, this specific surface area is equal to or greater than 20m
2/ g.More preferred specific surface area is equal to or greater than 25m
2/ g.The rough AlF that is used for the method according to this invention
3Generally have less than 100m
2The B.E.T. specific surface area of/g.Usually, this specific surface area is equal to or less than 75m
2/ g.More preferred specific surface area is equal to or less than 50m
2/ g.
Rough AlF
3Preferably mainly form by crystallization phases.Compare the crystallization phases content measured normally at least 60% by X-ray diffraction and to the relative intensity at peak.Preferred this content is at least 70%.Compare the crystallization phases content measured usually less than 100% by X-ray diffraction and to the relative intensity at peak.Preferred this content is at the most 85%.
As rough AlF
3When obtaining, be preferably the form of the hydrated aluminum oxide that is called boehmite, and can randomly contain silicon oxide (silica) composition of trace as raw-material alumina by fluoridizing of alumina.These alumina or silicon alumina are the commercially available prod, for example the Pural and the Siral grade product of Sasol (preceding title Condea) company.
In addition, if this catalyzer is used for fluidized-bed reactor, alumina has the size distribution that meets this purposes, as this area professional is known.
Except the patent of quoting, AlF
3Itself and preparation method thereof all be known in the art, for example referring to FR1.383.927.
In the method according to the invention, treatment temp preferably is equal to or greater than 330 ℃.More especially preferably be equal to or greater than 350 ℃ temperature.In the method according to the invention, treatment temp preferably is equal to or less than 420 ℃.More especially preferably be equal to or less than 400 ℃ temperature.
In the method according to the invention, the treatment time preferably is equal to or greater than 6 hours.More especially preferably be equal to or greater than 10 hours time length.In the method according to the invention, the treatment time was generally equal to or less than 50 hours.More especially preferably be equal to or less than 20 hours time length.
In the method according to the invention, processing pressure generally is equal to or greater than about 1 crust.Preferred atmosphere pressure (about 1 crust).In the method according to the invention, processing pressure generally is equal to or less than about 10 crust.Preferably treatment pressure is equal to or less than about 5 crust.
In the method according to the invention, be defined as the volume of reactor and the ratio of flow of process air amount the duration of contact of processing, it generally is equal to or greater than about 10 seconds.Be equal to or greater than about 30 seconds preferred duration of contact.In the method according to the invention, be generally equal to duration of contact or less than about 100 seconds.Be equal to or less than about 50 seconds preferred duration of contact.
In the method according to the invention, air-flow contains usually and is selected from least a of air, oxygen, hydrogen fluoride, halohydrocarbon or rare gas element.In rare gas element, what can mention especially is nitrogen and rare gas such as helium and argon.In halohydrocarbon, what can mention especially is hydrochloric ether, hydrofluoric ether and Chlorofluorocarbons (CFCs).In Chlorofluorocarbons (CFCs), preferred especially 1,1,1-three fluoro-2, the 2-ethylene dichloride and with isomer 1,1,2-three fluoro-1, the mixture of 2-ethylene dichloride.
If use the halohydrocarbon air-flow, it can be made up of halohydrocarbon substantially so, and perhaps it can be randomly diluted, for example uses inert gas dilution.
If plan to use active A lF
3Catalyzer makes the Chlorofluorocarbons (CFCs) isomerization, and so, in preferred embodiments, activation comprises with treating the activation treatment that isomerized Chlorofluorocarbons (CFCs) mixture carries out.
In particularly advantageous embodiment according to the inventive method, with air-flow handle comprise at least 2 treatment steps that use gas with various, described gas be preferably selected from mentioned above those.
In this embodiment, handle the treatment step that preferably includes at least one use anhydrous hydrogen fluoride stream with air-flow.In this case, the time length of handling with anhydrous hydrogen fluoride stream generally is equal to or greater than 4 hours.The time length of preferred this processing is equal to or greater than 6 hours.In this case, the time length of handling with anhydrous hydrogen fluoride stream generally is equal to or less than 16 hours.The time length of preferred this processing is equal to or less than 12 hours.
In particularly preferred embodiments, the temperature of handling with anhydrous hydrogen fluoride is about 350 ℃ ± 25 ℃ or 360 ℃ ± 25 ℃.
In first kind of particularly preferred mode implementing described embodiment, comprise with the air-flow processing
(a) handled at least 2 hours with inert gas,
(b) randomly, handle with anhydrous hydrogen fluoride stream, specifically as mentioned above.
(c) handle more than 3 hours with the air-flow that contains Chlorofluorocarbons (CFCs).
In this mode, (a) the preferably at least 4 hours time length of treatment step.(a) the generally at the most 12 hours time length of treatment step.(a) the preferably at the most 8 hours time length of treatment step.
In this mode, (c) the preferably at least 7 hours time length of treatment step.(c) the generally at the most 50 hours time length of treatment step.(c) the preferably at the most 25 hours time length of treatment step.Should be appreciated that, in this mode, discharge gas and can monitor, and become constant or during decline when the transformation efficiency of Chlorofluorocarbons (CFCs), just think that this processing finishes by GC.Handle if carry out HF in advance, finish this part and activate the needed time and will significantly shorten.In particularly preferred embodiments, (c) temperature of treatment step is about 350 ℃ ± 25 ℃.
In second kind of particularly preferred mode implementing described embodiment, comprise with the air-flow processing
(a) handled at least 2 hours with airflow,
(b) handled at least 4 hours with the anhydrous hydrogen fluoride air-flow.
In this mode, (a) the preferably at least 4 hours time length of treatment step.(a) the generally at the most 12 hours time length of treatment step.(a) the preferably at the most 8 hours time length of treatment step.
In the particularly preferred embodiment of this mode, (a) temperature of treatment step is about 390 ℃ ± 25 ℃.
In this mode, the time length of (b) treatment step that the use anhydrous hydrogen fluoride carries out as mentioned above.
Should be appreciated that the information in present method general description also is applicable to above-mentioned each specific embodiments.
The invention still further relates to active A lF
3Catalyzer, but its method according to this invention obtains.
The active catalyst that the method according to this invention obtains can be non-loaded and standby, perhaps can directly be used to make Chlorofluorocarbons (CFCs) such as HCFC-123a isomerization in same reactor.
In this case, suitably temperature regulation is arrived the needed value of acquisition ideal content of isomer.
The invention still further relates to the isomerization method of Chlorofluorocarbons (CFCs), Chlorofluorocarbons (CFCs) is contacted with active catalyst according to the present invention.
In isomerization method according to the present invention, Chlorofluorocarbons (CFCs) is preferably steam-like.
Can carry out in fixed-bed reactor or in the fluidized-bed reactor according to isomerization method of the present invention.The preferred streams fluidized bed reactor.
Can suitably utilize the isomerized hydrofluoric ether of isomerization method according to the present invention to comprise 1,1,2-three fluoro-1,2-ethylene dichloride, 1,1,2-trifluoro-1-chloroethane, 1,2-two fluoro-1-monochloroethane, 1-fluoro-1,2-ethylene dichloride, 1,1,3-three fluoro-1,3-propylene dichloride and 1,1,3,3-tetrafluoro-3-chloropropane etc.Preferred especially 1,1,2-three fluoro-1, the isomerization of 2-ethylene dichloride.Below illustrate specifically at 1,1,2-three fluoro-1, the isomerization reaction of 2-ethylene dichloride, but should be appreciated that this theme or conditions of similarity also are applicable to other Chlorofluorocarbons (CFCs).
In the preferred embodiment according to isomerization method of the present invention, the Chlorofluorocarbons (CFCs) that is incorporated in the reactor comprises 1,1,1-three fluoro-2,2-ethylene dichloride (123) and 1,1,2-three fluoro-1, the mixture of 2-ethylene dichloride (123a).
In this embodiment, the 123/123a mixture that joins in the reactor generally contains the 123a of 0.3wt% at least, with respect to the total amount of 123/123a mixture.This content usually is to be equal to or greater than about 0.5wt%.More frequently frequently, this content is equal to or greater than about 1wt%.In this embodiment, the 123/123a mixture that joins reactor generally contains the 123a of 50wt% at the most, with respect to the total amount of 123/123a mixture.This content is generally equal to or less than about 20wt%.More frequently, this content is equal to or less than about 15wt%.
In this embodiment, except 123 isomer, the organic raw material that is incorporated in the isomerization reaction can also contain a large amount of different compounds, for example desired as by product in 123 production processes those of preamble.Have been found that these compounds do not have a negative impact to isomerization method according to the present invention.Be incorporated into organic raw material in the isomerization reaction and can contain the by product of about 20wt% and 123 isomer of 80wt% at the most usually.
Surprisingly, the result who does not find isomerization reaction forms difference and significant difference is arranged because of the isomer of organic raw material.Can for example, under corresponding industrial condition, handle all possible isomer composition of for example fluoridizing the HCFC-123 of production enough neatly according to isomerization method of the present invention by tetrachloroethylene.If because the content of 123a is very high and make 123a fully not be converted into 123 in the raw material, this can overcome until reaching suitable feed composition by the circulating path of adjusting reactor so.
In isomerization method according to the present invention, organic raw material can randomly be used inert gas dilution, as mentioned above.If there is rare gas element, the rare gas element mark in the total air flow is generally at least 5 volume %.In this case, this mark is preferably at least 10 volume %.If there is rare gas element, the rare gas element mark in the total air flow is generally 90 volume % at the most.In this case, this mark is preferably 50 volume % at the most.
In isomerization method according to the present invention, temperature preferably is equal to or greater than 150 ℃.More preferred temperature is equal to or greater than 180 ℃.The most preferred temperature approximates or greater than 200 ℃.In isomerization method according to the present invention, temperature preferably is equal to or less than 260 ℃.More preferred temperature is equal to or less than 230 ℃.The most preferred temperature is equal to or less than 220 ℃.
The pressure of reactor does not have disadvantageous effect to isomerization reaction, and prerequisite is that it does not have height to causing Chlorofluorocarbons (CFCs) agglomerative degree under temperature of reaction.
In isomerization method according to the present invention, pressure generally is equal to or greater than about 1 crust.Preferred pressure is equal to or greater than about 2 crust.In isomerization method according to the present invention, pressure generally is equal to or less than about 10 crust.Preferred pressure is equal to or less than about 5 crust.
Though the pressure of reactor does not have a negative impact to the isomerization of 123a, be surprisingly found out that the high pressure of appropriateness helps the formation of unsaturated by product.Particularly, when moderately being higher than under the atmospheric pressure when preferably under the absolute pressure of 2-5 crust, implementing this method, unsaturated by product CFC-1112a (1,1-two chloro-2,2-difluoroethylene, CF
2=CCl
2) formation a large amount of reduce or even eliminate fully.This is an ideal, because CFC-1112a is not only poisonous but also be difficult to separate with HCFC-123.
Therefore, the invention still further relates to 1,1,2-three fluoro-1, the isomerization method of 2-ethylene dichloride wherein makes to be preferably 1,1 of steam condition, 2-three fluoro-1, the 2-ethylene dichloride contacts with isomerization catalyst under the 2-5 bar pressure.
The specific embodiments of the method according to this invention is corresponding with the specific embodiments according to isomerization method of the present invention.
Illustrate the present invention without limitation by following examples:
The activation of embodiment 1-catalyzer
Utilize the general fluorination process (embodiment) described in the United States Patent (USP) 6.187.280, obtain 9.0g finely powdered aluminum trifluoride sample by fluoridizing of SIRAL 1.5 silicon alumina, being encased in external diameter is in the tubular reactor of 3/8 inch (internal diameter is about 15mm), with the electric furnace heating, and in helium flow, temperature is raised to 350 ℃.
350 ℃ through after 4 hours, the HCFC-123 that will contain 11.9%123a joins in the raw material with the flow velocity of per minute 2.1scc (the cubic centimetre number under 20 ℃ and the barometric point)/min (0.8g/h).Pressure in the reactor is normal atmosphere, and helium and organic overall flow rate are 7scc/min.
To the sampling of expellant gas from reactor, and utilize GLC to analyze; Detected flow velocity every about 40 minutes, show that 123 transformation efficiency increases, carry out that transformation efficiency reaches maximum value after about 9 hours.
Two kind of 123 isomer all is converted to several disproportionation products: at the subsequent analysis that proceeds to 9 hours is typical case's composition of product when reaching maximum conversion rate:
HCFC-124
*9.7 weight %
HCFC-133a 1.7
CFC-114
* 3.6
CFC-113
* 0.6
HCFC-123a 0.3
HCFC-1237 6.8
CFC-1112
* 0.1
HCFC-1111
* 5.3
HCFC-122
* 1.0
Other is 0.9 years old
*Mixture of isomers
Remaining 123a/123 stable content is about 0.35%, the balance limit when this roughly is 350 ℃.
When the transformation efficiency when 123 reaches maximum value, temperature of reactor is reduced to the ideal isomerisation temperature.
The isomerization (fixed-bed reactor) of 123a in the time of embodiment 2-220 ℃
Continuity embodiment 1 drops to 220 ℃ with temperature of reactor, and continues sampling.Subsequent analysis to products therefrom shows that the formation of by product is negligible under this temperature, and remaining 123a/123 content is low to moderate about 500ppm.
HCFC-123a 0.05
HCFC-123 99.1
The CFC-1112a No data
Other is 0.85 years old
Selection rate (recording according to 123 the mark that is reclaimed) equals 99.2%; Consistence ground obtains The above results in entire test (about 6 hours), and the catalyzer non-inactivation.
The isomerization of 123a in the time of embodiment 3-200 ℃
Behind the certain interval of time, proceed test, utilize He/123 stream to make its temporarily reactivate, temperature of reactor is reduced to 200 ℃ then at 350 ℃ with embodiment 1 and 2 same catalyst of using.Under barometric point, the air-flow identical with embodiment 2 joined in the reactor.
In 4 hours time period, product is taken a sample.Their composition is stable substantially in entire test, and analytical results is as follows:
HCFC-123a 0.04
HCFC-123 99.5
The CFC-1112a No data
Other is 0.45 years old
Remaining 123a/123 is about 400ppm, is lower than embodiment 2, and selection rate also is increased to about 99.5%.
Carry out the isomerization of 123a with the HCFC-123a that contains a small amount of HCFC-123a in the time of embodiment 4-200 ℃
Only the content with asymmetric isomer in the HCFC-123 mixture becomes 3.8wt%, carries out embodiment 3 (using as carrying out activatory raw catalyst sample among the embodiment 1 in advance) again; Do not find significant difference among the result, the analytical results of product is as follows:
HCFC-123a 0.04
HCFC-123 99.6
The CFC-1112a No data
Other is 0.035 years old
Remaining 123a content is very low and total selection rate reaction is identical with embodiment 3 in the product.
Embodiment 5-and embodiment 4 are relatively
With the identical AlF that uses among the embodiment 1-4
3New sample be used for comparison test: like this, with the 10g catalyzer identical reactor of packing into, and under 350 ℃, in helium flow, only dewatered 1 hour, then under the condition identical with embodiment 4, activate with the HCFC-123 air-flow down at 350 ℃, but only carried out 2 hours.
Cool the temperature to 210 ℃ then, the He/123 air-flow (contain 3.8% 123a) identical with embodiment 4 added in the reactor.
The transformation efficiency of 123a descends very fast, carries out the 5 hours content in the after product gas and reaches 0.26%, is higher than expected value far away.
Therefore, omission also causes the useful life of catalyzer short as to make us being difficult to accepting according to activation of the present invention.
Embodiment 6-uses the fixed bed reaction of pelleted catalyst
Use pelleted catalyst in this embodiment.This catalyzer is particularly useful for plant-scale fixed-bed reactor.
With 400g (375 cubic centimetres) AlF
3Particle is encased in internal diameter 50mm, is equipped with in sintering bottom (frittedbottom) and the adiabatic tubular reactor.In this device, under so-called " thermal insulation " pattern, move reactor, this moment, heat offered reaction raw materials in interchanger before entering reactor.
In activation and isomerization test process, the pressure in the reactor all is barometric point.
Reactor is heated to 360 ℃ in stream of nitrogen gas, at first handle catalyzer in HF stream then, removes HF with nitrogen gas stream again, activates 20 hours with 123 air-flows at last under following condition:
350 ℃ of temperature, 0.266 mole/hour of 123 charging (41 Grams Per Hour), with 21 standard liters/hour nitrogen dilution; Be 33 seconds the nominal duration of contact under 350 ℃ and barometric point; HCFC-123 contains the asymmetric isomer of 0.3% (3000ppm).
When being transported to same airflow in the reactor, temperature of reactor is adjusted to 240 ℃ then, realize 40 seconds duration of contact like this.
To reaction product sampling and analysis, the content of finding remaining 123a is 0.025 (250ppm); It is constant that this result keeps during whole 30 hours test is carried out.
The isomerization of 123a in the embodiment 7-fluidized-bed reactor
400g (380 cubic centimetres) size distribution is suitable as the new AlF of fluid catalyst
3Be encased in the tubular reactor that 50mm is equipped with sintering bottom and be heated by resistive.In nitrogen gas stream, catalyzer is heated to 390 ℃ at the most, handled 4 hours with airflow at 390 ℃ then.Temperature with reactor is set at 360 ℃ then, interrupts airflow and replaces with the HF air-flow.After 10 hours, stop the HF air-flow, reactor is cleaned a few hours, simultaneously temperature is slowly dropped to 240 ℃ with nitrogen gas stream.
When temperature of reactor is stabilized in 240 ℃, the reaction mixture of following composition is joined in the reactor: the nitrogen of the HCFC-123 (containing 0.3% HCFC-123a) of 40.7 Grams Per Hours (0.266 mole/hour) and about 15 standard liters/hour (0.663 mole/hour).
Be 35 seconds the nominal duration of contact under temperature of reaction and barometric point.
To product sampling and utilize GC to analyze, its result is as follows:
1.61 moles of % of HCFC-124+124a
HCFC-123a 0.067
HCFC-123 97.47
CFC-1112a 0.33
Other is 0.52 years old
(20 hours) catalytic activity keeps stable in entire test, does not have the inactivation sign.The content of remaining 123a on average maintains about 700ppm, and selection rate is about 97.5%.
Embodiment 8
Do not do the test that any change continues embodiment 7 at a lower temperature.Under the situation of stopped reaction streams not even, the temperature of reactor is set in 210 ℃.Flow velocity is not with new temperature adjustment, so a little higher than embodiment 7 that becomes duration of contact.
Remaining 123a drops to 400ppm, and 124 conversion and 1112 formation also descend:
0.62 mole of % of HCFC-124+124a
HCFC-123a 0.034
HCFC-123 98.99
CFC-1112a 0.14
Other is 0.22 years old
During 70 hours tests are carried out, the remaining content kept stable of selection rate (about 99%) and the about 350-400ppm of 123a isomer.
Embodiment 9
Using in kind, activatory raw catalyst sample repeats embodiment 7; Under 240 ℃ temperature, the content of 123a is the 1.4wt% in flow of feed gas, under the condition identical with embodiment 7 HCFC-123 is joined in the reactor.Remaining 123a is stabilized in about 700ppm in HCFC-123.
2.23 moles of % of HCFC-124+124a
HCFC-123a 0.063
HCFC-123 96.26
CFC-1112a 0.55
Other is 0.90 years old
Embodiment 10
To be similar to the method described in embodiment 7 and 8, when the EO of embodiment 9, under the situation of stopped reaction streams not, the temperature of reactor is dropped to 210 ℃.Remaining 123a drops to about 400ppm, and content of by-products also reduces.
0.57 mole of % of HCFC-124+124a
HCFC-123a 0.038
HCFC-123 99.14
CFC-1112a 0.10
Other is 0.15 years old
During about 35 hours whole test of embodiment 10 was carried out, catalyzer did not show inactivation.
Embodiment 11-under condition of super atmospheric pressure, the 123a isomerization in the fluidized-bed reactor
The AlF that 400g is new
3Be encased in the testing apparatus identical with embodiment 7, and with embodiment 7 in identical method activate.
After the activation, temperature is set in 240 ℃, the pressure of reactor to be set at 3 bar absolute pressures (than high 2 normal atmosphere of normal pressure), and the mixture of 40.7 Grams Per Hours (0.266 mole/hour) HCFC-123 (containing 0.3% 123a) and about 63 standard liters/hour nitrogen is supplied in the reactor.
The results are as follows:
1.37 moles of % of HCFC-124
HCFC-123a 0.062
HCFC-123 98.42
CFC-1112a 0.20
Other is 0.05 years old
It is constant that these results keep in carrying out 160 hours process, and catalyzer does not show the inactivation sign in the meantime.
Clearly, the isomerization that pressure increases 123a does not have disadvantageous effect, and it is very effective for reducing by product 1112a, and described by product 1112a is poisonous and be undesirable compound.
Embodiment 12
Do not carrying out under the situation of catalyst regeneration, continuing the experiment of embodiment 1; Total flow of feed gas keeps identical but 123a content among the HCFC-123 is increased to 1.5wt%, and the result is as follows:
0.68 mole of % of HCFC-124
HCFC-123a 0.055
HCFC-123 98.90
CFC-1112a 0.25
Other is 0.12 years old
This embodiment shows, when using higher 123 raw materials of 123a content, the result is unaffected, and the remaining 123a in the product still reaches the balance limit.These results keep constant and finish until experiment, promptly begin to carry out more than 200 hours from embodiment 1.Also observing the side reaction that produces HCFC-124 reduces in time.
Embodiment 13
The catalyzer that is used for embodiment 1 and 12 utilizes air handling 4 hours and regenerates at 390 ℃, fluoridizes 12 hours with HF at 360 ℃ then.
After the regeneration, add 123/123a (the approximately 123a of 4000ppm) air-flow once more with pressure identical and feeding rate, and temperature of reaction is set in 220 ℃ with embodiment 1 and 12.Under this lower temperature, the remaining 123a decreased average in 123 keeps stable to 400ppm and in 140 hours entire test.1112a and other by products also reduce:
0.58 mole of % of HCFC-124
HCFC-123a 0.035
HCFC-123 99.29
CFC-1112a 0.06
Other is 0.04 years old
Embodiment 14
As mentioned above that embodiment 11-13 is used catalyst regeneration, the pressure in the reactor are set to 5 bar absolute pressures (4 crust gauge pressure).Temperature is 220 ℃.
In order to keep identical volume duration of contact, 123 and the nitrogen feed rate all to increase:
123=0.443 mole/hour=68 Grams Per Hours
Nitrogen=104 standard liters (under 20 ℃ and barometric point rise number)/hour
Obtain following result:
HCFC-124 0.05
HCFC-123a 0.06
HCFC-123 99.89
Other by product all is lower than the analysis threshold value.Therefore show that pressure has very favorable influence really.
Claims (15)
1. produce active A lF
3Catalyst based method, wherein under 300 ℃～450 ℃ temperature, with air-flow to rough AlF
3Handle more than 5 hours.
2. according to the process of claim 1 wherein that temperature is 350 ℃-400 ℃.
3. according to the method for claim 1 or 2, wherein rough AlF
3Handled 6-50 hour with air-flow.
4. according to each method among the claim 1-3, wherein rough AlF
3Contain the stoichiometry AlF of 95wt% at least
3
5. according to each method among the claim 1-4, wherein rough AlF
3Has 25m at least
2The B.E.T. specific surface area of/g.
6. according to each method among the claim 1-5, wherein air-flow contains at least a in air, hydrogen fluoride, halohydrocarbon or the gas.
7. according to each method among the claim 1-6, wherein handle and comprise at least 2 treatment steps that use gas with various with air-flow.
8. according to the method for claim 7, wherein comprise with the air-flow processing
(a) handled at least 4 hours with inert gas,
(b) randomly, handle with anhydrous hydrogen fluoride stream,
(c) handle more than 1 hour with the air-flow that contains Chlorofluorocarbons (CFCs).
9. according to the method for claim 7, wherein comprise with the air-flow processing
(a) handled at least 2 hours with airflow,
(b) handled at least 4 hours with anhydrous hydrogen fluoride stream.
10. active A lF
3Catalyzer, it obtains according to each method in the claim 1 to 9.
11. the isomerization method of Chlorofluorocarbons (CFCs) wherein makes Chlorofluorocarbons (CFCs) contact with catalyzer according to claim 10.
12. according to the method for claim 11, wherein Chlorofluorocarbons (CFCs) is a steam-like.
13. according to the method for claim 11 or 12, wherein Chlorofluorocarbons (CFCs) comprises 1,1,1-three fluoro-2,2-ethylene dichloride and 1,1,2-three fluoro-1, the mixture of 2-ethylene dichloride.
14. according to the method for claim 13, wherein isomerization is carried out under 180-220 ℃ temperature.
15.1,1,2-three fluoro-1, the isomerization method of 2-ethylene dichloride wherein makes to be preferably 1,1 of steam-like, 2-three fluoro-1, the 2-ethylene dichloride contacts with isomerization catalyst under the pressure of 2-5 crust.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP03102385A EP1502906A1 (en) | 2003-07-31 | 2003-07-31 | Process for activation of AIF3 based catalysts and process for isomerising hydrochlorofluorocarbons |
| EP03102385.6 | 2003-07-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1832908A true CN1832908A (en) | 2006-09-13 |
Family
ID=33522438
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2004800218063A Pending CN1832908A (en) | 2003-07-31 | 2004-07-27 | Process for activation of aif3 based catalysts and isomerization methods for chlorofluorocarbons |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20060189834A1 (en) |
| EP (1) | EP1502906A1 (en) |
| CN (1) | CN1832908A (en) |
| CA (1) | CA2534250A1 (en) |
| WO (1) | WO2005012213A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105294387A (en) * | 2015-10-22 | 2016-02-03 | 北京宇极科技发展有限公司 | Method for preparing chlorine fluorine cyclopentene isomeride |
| CN112929208A (en) * | 2021-01-25 | 2021-06-08 | 浙江大学 | Isomerous body decision method of mimicry virtual switch |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7485598B2 (en) | 2006-06-21 | 2009-02-03 | Arkema Inc. | High pressure catalyst activation method and catalyst produced thereby |
| KR101394583B1 (en) | 2006-10-03 | 2014-05-12 | 멕시켐 아만코 홀딩 에스.에이. 데 씨.브이. | Dehydrogenationhalogenation process for the production of C3-C6(hydro)fluoroalkenes |
| GB0706978D0 (en) | 2007-04-11 | 2007-05-16 | Ineos Fluor Holdings Ltd | Process |
| GB201615197D0 (en) | 2016-09-07 | 2016-10-19 | Mexichem Fluor Sa De Cv | Catalyst and process using the catalyst |
| GB201615209D0 (en) | 2016-09-07 | 2016-10-19 | Mexichem Fluor Sa De Cv | Catalyst and process using the catalyst |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL173393C (en) * | 1968-10-10 | 1984-01-16 | Montedison Spa | PROCESS FOR PREPARING COMPLETELY (CHLORINE) FLUOROUS ETHANE WITH SYMMETRICAL DISTRIBUTION OF THE FLUOR ATOMS OVER THE CARBON ATOMS. |
| JPH03284637A (en) * | 1990-03-31 | 1991-12-16 | Du Pont Mitsui Fluorochem Co Ltd | Isomerization of hydrochlorofluorocarbon |
| FR2669022B1 (en) * | 1990-11-13 | 1992-12-31 | Atochem | PROCESS FOR THE MANUFACTURE OF TETRAFLUORO-1,1,1,2-ETHANE. |
| IT1251957B (en) * | 1991-10-18 | 1995-05-27 | Ausimont Spa | PROCEDURE FOR ISOMERIZING 1,1,2-TRIFLUORO-1,2-DICHLOROETHANE TO 1,1,1- TRIFLUORO-2,2, -DICHLOROETHANE |
| IT1251951B (en) * | 1991-10-18 | 1995-05-27 | Ausimont Spa | PROCEDURE FOR PURIFYING 1,1,1-TRIFLUORO-, 2,2 DICHLOROETHANE FROM THE ISOMER 1,1,2-TRIFLUORO-1,2-DICHLOROETANO. |
| FR2700770B1 (en) * | 1993-01-27 | 1995-03-24 | Atochem Elf Sa | Process for the production of 1,1,1,2-tetrafluoro-2-chloroethane and pentafluoroethane. |
| FR2700766B1 (en) * | 1993-01-27 | 1995-03-24 | Atochem Elf Sa | Process for fluorination of perchlorethylene or pentachloroethane. |
| US5302766A (en) * | 1993-06-03 | 1994-04-12 | E. I. Du Pont De Nemours And Company | Isomerization process |
| WO1995011875A1 (en) * | 1993-10-28 | 1995-05-04 | Alliedsignal Inc. | Process for purifying 1,1-dichloro-2,2,2-trifluoroethane and 1-chloro-1,2,2,2-tetrafluoroethane |
| IT1291758B1 (en) * | 1997-05-22 | 1999-01-21 | Ausimont Spa | PROCESS FOR THE PREPARATION OF ALUMINUM FLUORIDE |
| IT1292007B1 (en) * | 1997-05-27 | 1999-01-25 | Ausimont Spa | PROCESS FOR THE PREPARATION OF HCFC-123 |
| US6432362B1 (en) * | 1999-10-06 | 2002-08-13 | Iowa State University Research Foundation, Inc. | Chemical sensor and coating for same |
-
2003
- 2003-07-31 EP EP03102385A patent/EP1502906A1/en not_active Withdrawn
-
2004
- 2004-07-27 US US10/565,957 patent/US20060189834A1/en not_active Abandoned
- 2004-07-27 CA CA002534250A patent/CA2534250A1/en not_active Abandoned
- 2004-07-27 WO PCT/EP2004/051624 patent/WO2005012213A1/en active Application Filing
- 2004-07-27 CN CNA2004800218063A patent/CN1832908A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105294387A (en) * | 2015-10-22 | 2016-02-03 | 北京宇极科技发展有限公司 | Method for preparing chlorine fluorine cyclopentene isomeride |
| CN105294387B (en) * | 2015-10-22 | 2017-04-05 | 北京宇极科技发展有限公司 | The method for preparing chlorine fluorine cyclopentene isomer |
| CN112929208A (en) * | 2021-01-25 | 2021-06-08 | 浙江大学 | Isomerous body decision method of mimicry virtual switch |
| CN112929208B (en) * | 2021-01-25 | 2022-02-11 | 浙江大学 | Isomerous body decision method of mimicry virtual switch |
Also Published As
| Publication number | Publication date |
|---|---|
| US20060189834A1 (en) | 2006-08-24 |
| WO2005012213A1 (en) | 2005-02-10 |
| CA2534250A1 (en) | 2005-02-10 |
| EP1502906A1 (en) | 2005-02-02 |
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